Diazotype material



United States Patent Ofiice 3,338,713 Patented Aug. 29, 1967 3,338,713 DIAZOTYPE MATERIAL Andreas Joseph Johannes Hendrickx and Adrianus Marie Petrus Hectors, Venlo, Netherlands, assignors to Chemische Fabriek L. van der Grinten N.V., Venlo, Netherlands, a corporation of Dutch law No Drawing. Filed Jan. 27, 1964, Ser. No. 340,534 Claims priority, application Netherlands, Feb. 1, 1963,

8 Claims. (CI. 96-91) The invention relates to diazotype material i.e. sheet material comprising a support carrying a layer of a diazonium compound, and more particularly to diazotype material containing a diazonium compound selected from a class of such compounds novel for the purpose. The diazotype material may, for example, be so-called onecomponent diazotype material which is developed with a liquid developer, so-called two-component diazotype material which is developed with the aid of ammonia vapour, or heat-developable diazotype material.

The invention further relates to a new class of diazonium compounds of use in the production of the said diazotype material.

In the diazotype process the diazonium compound 4-diazo-2,5-diethoxy-N-benzoylaniline has been applied on a large scale. Known materials are one-component diazotype material, two-component diazotype material, and heat-developable diazotype material, sensitized with this diazo compound. See British patent specification No. 347,430, British patent specification No. 815,005, and The Photographic Journal, 92B, 43-48 (1952).

Many other 4-diazo-2,5-dialkoxy-N-acylanilines, as Well as various 4-diazo-2,5-diaralkyloxy-N-acylanilines, have also been proposed for the sensitizing of diazotype materials. The acyl group of these compounds vary widely. In this connection, by acyl is to be understood the group -COR, in which R is hydrogen, or a substituted or non-substituted organic radical, such as alkyl, aralkyl, aryl, alkoxy, aralkyloxy and aryloxy, or a substituted amido group.

In the literature 4-diazo-2,5-di(alkylor aralkyl)oxy-N- acylanilines with e.g. the following acyl groups are found:

OOR Literature FormyL. British Patent Spec. 615,774. Acetyl Do. PropionyL Do. ButyryL Do. Phenacetyl British Patent Spec. 510,874. Benzoyl. British Patent Spec. 347,430. Naphthoyl. Do. Phenylthioacetyl British Patent Spec. 449,341. fl Naphthylthioacetyl Do. 4 ehlro-2 -rnethyl-phenylthioacetyl Do. Benzylthioacetyl Do. 4-diazo2,5-dieth0xy phenylamido- British Patent Spec. 620,038.

adipinyl. 4-diazo-2,5-diethoxy phenylann'do- Do.

phthalyl. Methoxycarbonyl British Patent Spec. 615,774. EthoxycarbonyL Do. PropoxycarbonyL Do. BenzyloxyearbonyL. Bn'tish Patent Spec. 520,304. 2-chloro-benzyloxycarbonyl D0. Phenethoxycarbonyl British Patent Spec. 539,031. B enzyloxyethoxycarb onyl D o. Phenoxyethoxycarbonyl Do. 4-chloro-phenoxyethoxy-carbonyl 4- British Patent Spec. 347,430.

diazo-2,5-di.methoxy phenylamidocarbonyl.

The 4-diazo-2,5-di(alkyl-, aralkyl-, or aryl)oXy-N- acylanilines have reasonable light-sensitivity and great coupling activity. The latter property makes them suitable for use in one-component diazotype material, and especially in one-component diazotype material that can be developed with weakly acid phloroglucinol developers. Compare: The Photographic Journal, 92B, 43-48 (1952).

The coupling activity of these diazonium compounds, however, is not so high that the development of diazotype materials sensitized with these compounds with the aid of the said weakly acid developers takes place as smoothly as desired. After application of the developing liquid some time elapses before the azo-dyestufls image becomes properly visible. Moreover, to obtain thorough development, the copies often have to be heated after the developing liquid has been applied.

Apart from this, the azo-dyestufifs formed from the 4- diazo-2,5-di(alkyl-, aralkyl-, or aryl)oXy-N-acylanilines and phlorogl-ucinol, using the said weakly acid developers, have rather low absorption for radiation from the near ultra-violet part of the spectrum, the radiation with the aid of which copies are made in the diazotype process. This implies that diazotype copies on translucent diazotype materials, sensitized with these diazonium compounds, are not particularly suitable for use as so-called intermediate copies, from which further copies are made.

In United States Patent No. 2,665,985 4-diazo-2',5'-di- (alkylor aralkyl) oxyphenyltriazines of the general Formula I are described, in which R stands for a hydrogen atom or an alkyl, aralkyl, or aryl radical and R has the meaning assigned to it above.

These compounds have lower coupling activity than the corresponding p-diazo-2,5-di(alkylor aralkyl)oXy-N- acylanilines. Consequently they are less suitable than the latter compounds for application in one-component diazo type materials for development with weakly acid developing liquids. The other properties of time two kinds of compounds are practically identical.

In Fiat Final Report 813, page 1267, the diazonium compound 4-diazo-2,5-dimethoXy-ptoulenesulphonamidobenzene is mentioned. Nothing is said about its properties. Tests with this compound have shown that it couples more slowly than the corresponding benzoylamino compound. For the rest its properties do not differ much from those of the last-mentioned compound.

Another known compound is the diazonium compound 4-diazo-2-alkoXy-N-benzoylaniline. This compound is not very light-sensitive and practically useless because of its poor stability. See Fiat Final Report 813, page 362.

According to the present invention there is provided diazotype material which comprises a support sheet carrying a layer of a diazonium compound of the general Formula II NzX wherein X is an anion, R is an alkyl (i.e., non-branched or branched alkyl), cycloalkyl or aralkyl radical, CO-R is an acyl group, R is an acylamino, alkylsulphonamido, aralkylsulphonamido, arylsulphonamido, or triazinyl group, and R, an alkyl, branched alkyl, cycloalkyl, aralkyl or aryl radical. According to a further feature of the invention there are provided, as a new class of diazonium compounds, the compounds of general Formula II just set forth. The diazonium compounds of Formula II have considerably higher coupling activity and, with polyvalent phenols such as phloroglucinol and resorcinol, form azo-dyestufis with greater absorption for U.V. radiation than the corresponding 2,5-di(alkyl-, aralkyl-, or aryl)oxy compounds (which compounds will hereinafter be referred to as 2,5-di-RO compounds). Consequently diazotype material sensitized with these new diazonium compounds develops much more rapidly than diazotype material sensitized with the corresponding 2,5-di-RO compounds and, when polyvalent phenols are used as azo components, often yields copies with azo-dyestufis having better absorption for U.V. radiation.

The diazotype material according to the invention preferably is a one-component diazotype material. Upon development with the conventional weakly acid phloroglucinol developers it yields copies with dark-red to brown azo-dyestuff images; upon development with the conventional weakly alkaline phloroglucinol developers it yield copies with lighter-coloured, orange-red to brown azo-dyestuff images.

It may, however, also be two-component diazotype material. In that case a slowly coupling compound, such as 7'-hydroxy-1,2',4,S-naphthimidazole, 2-hydroxynaphthalene-3,6-disulphonic acid, and 7-hydroXy-1-biguanidinonaphthalene, may be included as azo-coupling component.

The diazotype material according to the invention may be heat-developable diazotype material, e.g. of the type described in British patent specification No. 815,005 and in British patent application No. 47,343/ 62.

The diazotype material according to the invention may contain an opaque support, such as opaque white paper or opaque linen, or a transparent support, such as tracing paper, tracing linen, cellulose-ester foil, polyester foil, transparentized paper and the like. The diazonium compound may be applied direct to the support or may be present in a hydrophilic or hydrophobic film layer which may or may not be attached to the support by means of one or more sub-layers.

Below is given an enumeration, though not a complete one, of diazonium compounds which can be applied in the diazotype material according to the invention 4-diazo S-N-acetyl N-methylamino 2-methoxy N-acetylaniline 4-diazo S-N-acetyl N-methylamino 2-4-chloro(phenoxy) N-acetylaniline 4-diazo -N-octanoyl N-methylamino Z-ethoxy N-acetylaniline 4-diazo S-N-acetyl N-ethylamino Z-methoxy N-phenacetylaniline 4-diazo 5-N-acetyl N-methylamino 2-n-propoxy N-benzoylaniline 4-diazo S-N-acetyl N-methylamino 2-methoxy N 2',4'-dichlorobenzoyl) aniline 4-diazo S-N-acetyl N-methylamino 2-cyclopentyloxy N-benzoylaniline 4-diazo S-N-acetyl N-methylamino 2-methoxy N-naphthoyl- 1 -aniline 4-diazo 5-N-acetyl N-methylamino 2-n-butoxy N-benzoylaniline 4-diazo S-N-acetyl N-methylamino 2-isobut0xy N- (2-chlorobenzoyl) aniline 4-diazo S-N-acetyl N-methylamino 2-(4'-chlorophenoxy) N benzoylaniline 4-diazo 5-N-propionyl N-propylamino Z-benzyloxy N-butyrylaniline 4-diazo 5-N-acety1 N-methylamino Z-methoxy N-ethoxycarbonylaniline 4-diazo S-N-propionyl N-isoamylamino 2-ethoxy N-propoxycarbonylaniline 4-diazo S-N-butyryl N-ethylamino Z-methoxy N-benzyloxycarbonylaniline 4-diazo S-N-acetyl N-methylamino 2-methoxy N-phenoxycarbonylaniline 4-diazo S-N-acetyl N-isopropylamino Z-methoxy N-benzoylaniline 4-diazo S-N-a-cetyl N-n-butylamino Z-methoxy N-benzoylaniline 4-diazo S-N-acetyl N-n-hexylamino Z-methoxy N-benzoylaniline 4-diazo S-N-acetyl N-cyclohexylamino Z-methoxy N-benzoylaniline 4-diazo S-N-acetyl N-benzylamino Z-methoxy N- benzoylaniline 4-diazo S-N-formyl N-methylamino 2-methoxy N-benzoylaniline 4-diazo S-N-chloroacetyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo 5-N-isobutyryl N-methylamino Z-methoxy N-benzoylaniline 4-diazo 5-N-isobutyryl N-methylamino 2-isopropoxy N-benzoylaniline 4-diazo S-N-butyryl N-Inethylamino Z-methoxy N-benzoylaniline 4-diazo S-N-hexanoyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-phenylacetyl N-methylarnino Z-methoxy N-benzoylaniline 4-diazo S-N-benzoyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-furoyl-(Z) N-methylamino 2-methoxy N-benzoylaniline 4-diazo S-N-ethoxycarbonyl N methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-isobutyloxycarbonyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-benzyloxycarbonyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-phenoxycarbonyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo 5-N-cyclohexyloxycarbonyl N-methylarnino 2-methoxy N-benzoylaniline 4-diazo 5-N-phenoxy-ethoxycarbonyl N-methylamino Z-methoxy N-benzoylaniline 4-diazo S-N-furfuryloxycarbonyl N-methylamino 2-methoxy N-benzoylaniline N,N-bis-(4-diazo S-N-acetyl N-methylamino 2-methoxyphenyl)-urea N-phenyl N-(4-diazo S-N-acetyl N-methylamino 2-methoxyphenyl) -urea oxalic-acid-bis-(N-methyl N-2'-diazo 5-benzoylamino 4-methoxyphenylamide) adipic acid-bis-(N-methyl N-2'-diazo 5-benzoylamino 4-methoxyphenylamide) adipic acid-bis-(4-diazo 5'-N-acetyl N-methylamino 2'-methoxyphenylamide) 4-diazo 5 -N-acetyl N-ethylamino Z-methoxy p-toluenesulphonamidobenzene 4-diazo 5-Nacetyl N-methylamino Z-n-propoxy methylsulphonamidozenzene l-(4-diazo 5 -N-acetyl N-methylamino 2'-rnethoxyphenyl)-2-arnino 4-imino G-methyltriazine (1,3,5). The diazonium compounds are applied in the form of their diazonium salts, e.g. diazonium chlorides, sulphates,

nitrates and metal chloride double salts (e.g. diazonium chlorozincates, chlorostannates), borofluorides, and the like. They can be applied separately in the diazotype material according to the invention or be mixed together.

Naturally they can also be used in admixture with diazonium compounds of other types. However, according as these mixtures have a lower content of diazonium compounds according to the description given, the diazotype material according to the invention, prepared with these mixtures, will present the advantages described to a smaller degree. The diazonium compounds that can be used in the diazotype material according to the invention can all be prepared by starting from the 4-chloro 2- aminophenolalkyl, branched alkyl, cycloalkyl, aralkyl, or aryl ethers. The 4 chloro 2-amino-phenolalkyl, branched alkyl, cycloalkyl, and aralkylethers can be obtained from 4-chlorophenol by introducing into this product a nitro group in ortho-position relative to the hydroxyl group, and etherifying the hydroxyl group and reducing the nitro group to an amino group.

The 4-chloro 2-aminophenolaryl ethers are obtained by fusing 2,5-dichloronitrobenzene with a hydroxyaryl compound and potassium hydroxide and reducing the nitro group.

The amino group of the 4-chloro Z-aminophenolalkyl, branched alkyl, cycloalkyl, aralkyl, or aryl ether is (a) acylated with e.g. a carbohalide or an ester or chloroformic acid, or

(b) Converted into a sulphonamido group (alkyl-, aralkylor aryl-substituted) with the aid of an organic sulphochloride, or

(c) Brought into reaction with dicyanodiamide to form a biguanidino group, whereupon the ring closure to form a triazinyl ring with an organic carboxylic acid or its anhydride takes place.

Thus the ether of 4-chloro 2-(acylamino, sulphonamido, or triazinyl) phenol is obtained. This ether is nitrated, and its chlorine atom is then substituted by a monoalkyl, branched alkyl, cycloalkyl, or aralkylamino group, which is subsequently acylated.

The 4-acyl, 4-sulphonamido, or 4-triazinyl Z-N-acyl N- (alkyl, branched alkyl, cycloalkyl, or aralkyl)amino 5 (alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxynitrobenzene thus formed is reduced to the corresponding amine, and then a diazonium compound is produced from it in the usual way. 1

A preferred form of diazotype material according to the invention is that containing a diazonium compound of the general Formula II, in which X is an anion, R stands for a non-branched alkyl group having at most five C- atoms, -COR for an acyl group, R for an acylamino or triazinyl group, and R for an alkyl, aralkyl or aryl radical. This diazotype material not only couples more actively, but has moreover considerably higher light-sensitivity than diazotype material sensitized with a corresponding 2,5-di-RO compound.

A further preferred form of diazotype material according to the invention is one-component diazotype material containing a diazo compound of the general Formula III in which X is an anion and R stands for a non-branched alkyl group having at most five C-atoms, R for a hydrogen atom or an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group, R for an alkyl, alkoxy, benzyl, benzyloxy, phenyl, or phenoxy group, and R for an alkyl or benzyl radical. Such diazotype material is properly lightsensitive and develops very rapidly when weakly acid phloroglucinol developers are used. Moreover, upon development with the above-mentioned developers it yields copies with azo-dyestufrs which often have been absorption for U.V. radiation than diazotype material sensitized with the corresponding di-RO compounds. Consequently the diazonium compounds according to the above general Formula HI are eminently suitable for use in transparent one-component diazotype material for development with weakly acid phloroglucinol developers.

Among these diazonium compounds those in which R is an alkoxy, benzyloxy or phenoxy group are outstanding; they are more stable that the corresponding diazonium compounds in which R is an alkyl, benzyl, or phenyl radical, and the azo-dyestuffs formed from them are darker and have better Water-fastness than those formed from the corresponding diazonium compounds referred to above, so that with the diazonium compounds in which R is an alkoxy, benzyloxy, or phenoxy group a diazotype material of good stability can be made, yielding copies with a fairly dark-brown azo-dyestulf image which shows no or only very little bleeding of the azo-dyestulf upon development. Since, moreover, the azo-dyestulf has good absorption for U.V. radiation, these diazonium compounds are eminently suitable for the sensitizing of transparent diazotype materials.-The copies show a dark, very legible image with good absorption for U.V. radiation, and thus are "very suitable for use as transparent intermediate originals.

In Fiat Final Report 813, pages 86, 87, and 1095, benzene diazonium compounds are described which have a N-acetyl N-methyl-a-mino group in ortho-position. Furthermore they may carry methyl or methoxy substituents. These diazonium compounds have practically no light-sensitivity and are very unstable, they couple actively, whilst forming light-coloured, yellow to red azo-dyestulfs. With these diazonium compounds no diazotype material that is suitable in practice can be made.

In the diazotype material according to the invention the auxiliary agents commonly used in diazotype materials can be applied, e.g. acids, such as citric acid, tartaric acid, and boric acid; metal salts, such as zinc chloride, nickel sulphate and alum; stabilizers, such as benzene and naphthalene diand trisulphonic acids, p-phenol sulphonic acid and their Water-soluble salts, and urea; substances which increase the developing speed, such as glycerol; substances which improve the water-fastness and/ or the shade of the azo-dyestulf, such as 7'-hydroxy-1',2',4,5,-naphthimidazole and 2-hydroxymethyl benzimidazole; particles for improving the surface of the support, such as silica, aluminum oxide, rice starch ,and polyvinyl acetate particles; binders, such as polyvinyl alcohol, methylcellulose, and starch ethers.

The phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity. Three weakly acid phloroglucinol developers and one weakly alkaline phloroglucinol developer are described below, which are employed in practice and which are used for development in the examples following hereafter.

Developer A is a solution of: Phloroglucinol g 4 Acetoacetanilide g 0.1

2-ethyl l-hexanosulphate Tergitol 08 (from Union Sodium salt of butylnaphthalene sulphonic acid Sorbit P (from Geigy Chem. Corp, Ardsley, N.Y.,

U.S.A.) g 2 Sodium formate g 14 Sodium benzoate g 22 Trisodiu'm citrate (2 aq.) g 49 Citric acid g 1.2 Water ml 1000 The pH of this liquid is 6.5.

Developer C is a solution of:

Potassium salt of hydroquinone-mono sulpho 10 acid g 1 Sorbitol g Beet sugar g 15 Potassium tetraborate (5 aq.) g 50 [sopr-opylnaphthalene sulponic acid g 1.5 Water ml 1000 The pH of this liquid is approximately 9.5.

The following examples will serve to illustrate the production and the use of the new diazonium compounds according to the invention:

Example I White base paper of weight 80 g./m. for the diazotype process, which has been pre-c-oated with an aqueous silica dispersion and then dried, is sensitized with a liquid containing: 4-(4-methylphenyl)-sulphonylamino S-methoxy, 2-

N-methyl N-acetylaminobenzene diazonium chloand dried.

On the light-sensitive layer an intermediate layer is formed by spreading on it a solution of:

Polyvinyl acetate Vinnapas U.W. 50 g 100 Trichloroethylene ml 1000 and drying.

On the intermediate layer a top layer is applied with the aid of a liquid containing:

2,3-dihydroxynaphthalene g 5 Non-colloidal silica g 20 N-acyl N-2-hydroxyethylethylene diamine Nal camine A.12 (from Nalco Chemical Co., Chicago 38, Ill., U.S.A.) g 46 Ligroin ml 1000 The dried light-sensitive material is image-wise exposed under a transparent Indian-ink drawing until the diazo compound under the image-free portions of the drawing has bleached out, and is then developed by guiding it over a heated roller having a temperature of about 140 C., the back of the sheet contacting the roller surface.

The copy shows a red-brown image on a white background.

If in the above-mentioned sensitizing liquid an equivalent quantity of the corresponding 4-(4'-methyl phenyl) sulphonylamino 2,5-diethoxybenzene diazonium compound had been used, the light-sensitive material obtained would have been considerably less light-sensitive and would have had a lower developing speed.

The diazonium compound used in the example is prepared as follows: S-chloro 2-methoxyaniline is tosylated with p-tosyl chloride and then nitrated. The S-methoxy 4-p-tosylamino 2-chloro l-nitrobenzene is brought into reaction with monomethylamine, and the reaction product thus obtained is acetylated. The melting point of the 5-methoxy 4-p-tosylamino Z-N-acetyl N-methylamino l-nitrobenzene thus obtained is 190 C. This nitro compound is catalytically reduced to the corresponding amine, which is then diazotized. The resulting diazonium compound is obtained in the form of the zinc chloride double salt.

Example II White base-paper of weight 50 g./m. for the diazotype process is transparentized in the usual way by treating it with a resin solution in an organic solvent and drying it, and is then sensitized with a solution of 4-benz0ylarnino Z-N-acetyl N-methylamino S-ethoxybenzene diazonium chloride, zinc chloride double salt g 50 Tartaric acid g" 3 Boric acid g 1 Sodium salt of naphthalene 1,3,6-trisulphonic acid g 40 Gum arabic g 2.5 Rice starch g 120 Vinnapas H.60 ml 40 Water ml 1000 A sheet of the dry light-sensitive material is imagewise exposed under a transparent pencil-drawing until the diazonium compound under the white portions of the original has largely bleached out and is then developed with the developer B described above, according to the socalled thin-layer method.

The copy shows a brown image on a foggy light-brown background.

The image has good absorption for U.V. radiation, so that the copy is very suitable for use as an intermediate original for making further copies on diazotype material.

If in the above-mentioned sensitizing liquid an equivalent quantity (about 4 g.) of 4-benzoylamino 2,5-diethoxybenzene diazonium chloride, zinc chloride double salt, had been used, the light-sensitive material obtained Would have been considerably less light-sensitive, would have had a lower developing speed, and would have yielded a copy with a dark-brown image on a red-brown background, which image would have had smaller absorption for U.V. radiation.

The diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide to form 2-nitro 4-chloro l-ethoxybenzene. The nitro group of this product is catalytically reduced, after which the free amino group is benzoylated. The 2-benzoylamino 4-chloro l-ethoxybenzene thus formed is nitrated, subsequently brought into reaction with monomethylamine, and then acetylated, by which means S-ethoxy 4-benzoylamino Z-N-acetyl N-methylamino l-nitrobenzene is obtained. The melting point of this nitro compound is l94-l95 C. After the nitro group of this compound has been catalytically reduced and the amine thus formed has been diazotized, the diazonium compound is obtained in the form of the zinc chloride double salt.

Example 111 A cellulose acetate film layer of weight about 20 g./m. applied on natural tracing paper of weight about g./ m. is superficially hydrolysed to a depth of about 4 ,u. and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

4-benzoylamino 2 N hexanoyl N methylamino S-methoxybenzene diazonium chloride, zinc chloride double salt g 34 Citric acid g 4 Gelatin g 2 Ethanol (96%) ml 250 Water ml 750 and then dried.

A sheet of the dry transparent diazotype paper is imagewise exposed under a transparent ink drawing until all the diazo compound under the image-free portions of the original has bleached out and is then developed with developer B according to the thin-layer method. The transparent copy obtained shows a brown image, which has fairly good absorption for U.V. radiation.

If one compares the transparent diazotype paper, made as described above, with the same material in which, instead of the above-mentioned diazonium compound, 4-benzoylamino 2,5-dimethoxy benzene diazonium chloride, zinc chloride double salt, has been used for the sensitizing, it appears that the last-mentioned diazotype material is less light-sensitive and has a lower developing speed. Moreover it yields copies with violet-brown azodyestuff images.

The diazonium compound used according to the example is prepared as follows: 5-ch1oro 2-methoxyaniline is benzoylated and then nitrated. The 5-chloro 4-nitro 2- methoxy N-benzoylaniline thus formed is brought into reaction with monomethylamine and then acetylated with hexanoyl chloride. The S-methoxy 4-benzoylamino 2-N- hexanoyl N-methylamino l-nitrobenzene melts at 117- 119 C. The nitro group of this compound is catalytically reduced and the amine thus formed is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.

Example IV A cellulose acetate film layer of weight about 20 g./m. applied on a natural tracing paper of weight about 80 g./m. is superficially hydrolysed to a depth of about 4 and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

4-benzoylamino 2-N-acetyl N-n-butylamino S-methoxybenzene diazonium chloride, zinc chloride and then dried.

A sheet of the dry transparent diazotype paper is imagewise exposed and developed as described in Example III. The copy thus obtained shows a violet-brown image that has good absorption for U.V. radiation.

If a copy is made in the same Way on similar transparent diazotype paper, which is obtained when in the above-mentioned solution 4-benzoylamino 2,5-dimethoxybenzene diazonium chloride, zinc chloride double salt, is used instead of the diazonium compound mentioned, it appears that the diazotype material thus produced is less light-sensitive, develops more slowly, and yields copies with azo-dyestufi images having smaller absorption for U.V. radiation.

The diazonium compound used in the example is prepared as follows: 5-chloro 2-methoxyaniline is converted into 5-chloro 4-nitro2-methoxy N-benzoylaniline as described in Example III.

This product is then brought into reaction with mono-nbutylamine and acetylated to form 5-methoxy 4-benzoylamino 2-N-acetyl N-n-butylamino l-nitrobenzene, which compound melts at 145-146" C. In the Way described in Example III this nitro compound is converted into the diazonium compound, which is obtained in the form of the zinc chloride double salt. I

Example V By immersion, transparent cloth type Sub./ 0/ 86 (from Red Bridge Book Cloth Company, Red Bridge, Ainsworth, Bolton, England) is coated with a layer of weight about 70 g. /m. of the following liquid:

Polystyrene copolymer Lutron X 820 (from Monsanto Chemical Company, Plastics Division,

Springfield 2, Mass., U.S.A.) g Polyvinyl acetate Rhodopas H.V.2 (from Rhone- Poulenc, Paris, France) g 30 Ethyl acetate ml 50 Ethanol (96%) ml 900 After drying, a layer of weight about 80 g./m. of the liquid mentioned below is applied on the hydrophobic adhesive layer thus formed:

York 20, U.S.A.) g 5 Ethanol (96%) l 500 Water ml 500 After drying, a' hydrophilic polyvinyl acetate layer (thickness about 4.5 microns) is present on the adhesive layer.

The hydrophilic poylvinyl acetate layer is sensitized with a solution of:

' 4-acetylamino 5-ethoxy Z-N-octanoyl N-methylaminobenzene diazonium chloride, zinc chloride double salt g 42 Tartaric acid g 5 Gelatin g 2 Ethanol (96%) ml 250 Water ml 750 and dried.

The hydrophilic light-sensitive layer obtained after drying contains about 0.9 millimol of diazonium compound per in. sensitized surface.

A sheet of the transparent diazotype linen thus obtained is image-wise exposed and developed as described in Example II. The copy thus obtained shows a darkbrown azo-dyestuff image on a foggy light-brown back ground. The azo-dyestuff image has good absorption for U.V. radiation.

Consequently the copy is eminently suitable for use as an intermediate original for making further copies.

If in the above sensitizing liquid a corresponding quantity of 4-acetylarnino, 2,5-diethoxybenzene diazonium chloride, zinc chloride double salt, had been used, the light-sensitive material thus obtained would have been considerably less light-sensitive, would have had a lower developing speed, and would have yielded a copy with a violet-brown image on a somewhat violet background, which image would have had smaller absorption for U.V. radiation.

The diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide ,to form 2-nitro 4-chloro l-ethoxybenzene. The nitro group of this compound is catalytically reduced, after which the amino group thus obtained is acetylated. The 2-acetylamino 4-chloro l-ethoxybenzene thus formed is nitrated, brought into reaction with monoethylamine, and then acylated with octanoyl bromide, by which reaction S-ethoxy 4-acetylamino 2-N- octanoyl N-methylamine l-nitrobenzene is obtained. The melting point of this compound is -127 C. After the nitro group of this compound has been reduced and the amine thus formed has been diazotized, the diazonium compound is obtained in the form of the zinc chloride double salt.

Example VI A clear cellulose acetate film of 150 g./m. with an acetyl content of approximately 2.5 acetyl groups per unit of glucose of the cellulose acetate is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

1-(4'-diazo '-N-acetyl N-methylamino 2'-methoxy phenyl) 2-amino 4-imino 6-methyl 1,3,5-triazine g 80 Tartaric acid g 4 Potassium salt of benzene 1,3-disulphonic acid g Gum arabic g 1 Ethanol (96%) ml 250 Water ml 750 and dried.

The diazotype material thus obtained is very light-sensitive and has a high developing speed. A sheet of this diazotype material is exposed under a transparent India ink drawing until all the diazonium compound under the image-free portions of the drawing has bleached out, and is then developed with developer B. The copy shows a brown image on a crystal-clear background. The copy thus obtained is eminently suitable for use as an intermediate original for making further copies. The azo-dyestufr image has good absorption for U.V. radiation.

The diazonium compound used in the example is prepared as follows: 5-chloro 2-rnethoxyaniline (HCl salt) is brought into reaction with dicyanodiamide, by which means 5-chloro Z-methoxy l-biguanidinobenzene is obtained. With the aid of acetic anhydride this compound is converted into 1-(5-chloro 2-methoxy phenyl) Z-amino 4-imino 6-methyl triazine (1,3,5), which compound is nitrated, after which the product thus obtained is brought into reaction with monomethylamine. In this way 1-(4- nitro 5'-N-methylamino 2'-methoXy)-2-amino 4-imino 6- methyl triazine is obtained, which compound melts at 298-300 C. This product is acetylated, after which the nitro group is reduced. The amino compound is diazotized and the diazonium compound thus prepared is obtained in the form of the above-mentioned salt.

Example VII A clear cellulose acetate film of weight 150 g./m. with an acetyl content of about 2.5 acetyl groups per unit of glucose of the cellulose acetate is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

methoxyphenyl urea-bis (zinc chloride double salt) g 42.5 Citric acid g 7.5 Sodium salt of naphthalene 1,3,6-trisulphonic acid g 40 Ethanol (96%) ml 500 Water ml 500 and dried.

The hydrophilic light-sensitive layer obtained after drying contains about 0.5 millimol of diazonium compound per m. of the sensitized surface.

A sheet of the diazotype material thus prepared is image-wise exposed and developed as described in Example III. The copy thus obtained shows a red-brown image on a crystal-clear background. The aZo-dyestuff image has good absorption for UV. radiation.

The diazonium compound used in the example is prepared as follows: 4-methoxyaniline is nitrated to form 4- methoxy 3-nitroaniline, and With p-tosyl chloride this product is converted into 4-methoxy 3-nitro N-p-tosylaniline, which is methylated with dimethyl sulphate, after which it is hydrolysed to 4-methoxy 3-nitro N-methylaniline. This compound is acetylated and its nitro group is reduced, by which means Z-methoxy S-N-acetyl N- methylaminoaniline is obtained. This compound is brought into reaction with phosgene. Thus N,N'-bis(2-methoxy 5- N-acetyl N-methylamino phenyl)urea is formed, from which, upon nitration, N,N'-bis(2-methoxy S-N-acetyl N-methylamino 4-nitrophenyl)urea is obtained, the latter compound melting at 279283 C.

This nitro compound is converted into the above-mentioned diazonium salt in the usual way.

Example VIII Transparent linen for the diazotype process, e. g. Winterbottom NFSB cloth (from The Winterbottom Book Cloth 00., Manchester 2, England), is sensitized with a solution of:

Zinc chloride double salt of 4-phenacetylamino 5- methoxy Z-N-acetyl N-ethylaminobenzene diazoand dried.

A sheet of the diazotype linen thus obtained is imagewise exposed as described in Example 111 and developed with developer C.

The copy obtained shows a brown azo-dyestuff image.

If in the above sensitizing liquid an equivalent quantity of 4-phenylacetylamino 2,5-dimethoxybenzene diazoium chloride, zinc chloride double salt, had been used, the light-sensitive material obtained would have been considerably less light-sensitive, would have had a lower developing speed, and would have yielded a copy with a dark-brown image.

The diazonium compound used in the example is prepared as follows: 5-chloro 2-methoxyaniline is phenacetylated and then nitrated. The 5-chloro 4-nitro Z-methoxy N-phenacetylaniline thus formed is brought into reaction with monoethylamine and then acetylated. The S-methoxy 4-phenacetylamino Z-N-acetyl N-ethylamino l-nitrobenzene melts at 158 C. The nitro group of this compound is reduced to amino group and the amine is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.

Example IX White base paper of weight g./m. for the diazotype process is sensitized with a liquid containing:

Zinc chloride double salt of 4-benzoylamino S-methoxy Z-N-benzyloxycarbonyl N-rnethylamino ben- A sheet of the diazotype paper thus obtained is imagewise exposed under a transparent ink drawing until all the diazonium compound under the image-free portions of the drawing has bleached out and is then developed with developer A. The copy obtained shows a brown image on a clear white background.

If in the above sensitizing liquid an equivalent quantity of 4-benzoylamino, 2,5-dimethoxybenzene diazonium chloride, zinc chloride double salt, had been used, the light-sensitive diazotype paper obtained would have been considerably less light-sensitive and would have had a lower developing speed.

The diazonium compound used in the example is pre- Example X A cellulose acetate film layer of weight about 20 g./m.

applied on natural tracing paper of weight about 80 g./m. is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

Zinc chloride double salt of 4-benzoylamino S-n-butoxy 2-N-aoetyl N-methylaminobenzene diazonium chloride g 56 Alum g 8 Sodium salt of naphthalene 1,3,6-trisulphonic acid Gum arabicg 1 Ethanol (96%) ml 300 Water ml 700 and dried.

A sheet of dry the light-sensitive material is image-wise exposed under 'atransparent pencil drawing until the diazonium compound under the image-free portions of the original has largely bleached out and is then developed with developer B. The copy shows a brown image on a foggy light-brown background. The image has good absorption for UV. radiation, so that the copy is very suitable for use as an inter-mediate original.

If in the above sensitizing liquid an equivalent quantity of 4-benzoylarnino 2,5 di-n-butoxy benzenediazonium chloride, zinc chloride double salt, had been used, the light-sensitive material obtained would have been considerably less light-sensitive, would have had a lower developing speed, and would have yielded a copy with a black image on a foggy grey background, which image would have had smaller absorption for UV. radiation.

The diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and butylated with n-butyl bromide. The nitro group of the product obtained is reduced and the amino compound resulting therefrom is benzoylated. The Z-benzoylamino 4-chloro 1-butoxyben zene thus formed is nitrated, brought into reaction with" monomethylamine, and then acetylated. Thus butoxy 4-benzoylamino 2-N-acetyl N-:methylamino l-nitrobenzene is obtained, which compound .melts at 120- 122 C. From this nitro compound the above-mentioned a n Salt s. f m d,

'ExampleXI ,A .celluloseacetatefilm layer .of about 20 g./m. applied on natural tracing paper of about 80 g./m. is super? ficially-hydolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:

Zinc chloride double salt of 4-ethoxy carbonylamino 5-meth0xy'2-N-acetyl N- methylaminobenzene di- Water ml 700 and dried.

A sheet of the dry light-sensitive material is image-wise exposed under a transparent pencil drawing until the diazonium compound under the image-free portions of the original has largely bleached out and is then developed with developer D. The copy shows a brown image on a foggy light-brown background. The image has good ab sorption for UV. radiation, so that the copy is very suitable for use as an intermediate original.

If in the above sensitizing liquid an equivalent quantity of 4-ethoxycarbonylamino, 2,5-dimethoxy-benzene diazonium chloride, zinc chloride double salt, had been used, the light-sensitive material thus obtained would have been considerably less light-sensitive and would have had a lower developing speed.

The diazonium compound used in the example is prepared as follows: S-chloro 2-methoxyaniline is acylated with the ethyl ester of chloro-fonnic acid and then nitr-ated. The S-ch'loro 4-nitro 2-methoxy N-ethoxycarbonylaniline thus formed is then brought into reaction with monomethylamine and acetylated. The 5-rnethoxy 4- ethoxycarbonylamino 2-N-acetyl N-methylamino l-nitrobenzene melts at 202-203" C. From this nitro compound the corresponding diazonium compound is prepared in the usual way, said compound being obtained in the form of the zinc chloride double salt.

Example XII A transparentized rag paper, such as transparentized rag paper grade 506 (from Plastic Coating Corp, Holyoke, Mass., U.S.A.), is sensitized with a solution of:

A sheet of the diazotype material thus obtained is image-wise exposed and developed as described in Example X. The copy shows a brown image on a foggy light-brown background The image has good absorption for UV. radiation and consequently is very suitable for use as an intermediate original. I

, The diazonium compound used in the example is prepared as follows: S-methylamino 4-nitro Z-methoxy N- benzoylaniline (see Example IX) is brought into reaction with adipyl chloride, N,N'-dimethyl N,N'-bis(2'-nitro 4- methoxy. 5-benzoylaminophenyl) adipic diamide thus be ing formed, which compound melts at 229-231" C. The nitro groups of this compound are reduced, the amino groups diazotized, and the bis-diazonium compound is obtained in the form of the zinc chloride double salt.

Example XIII White paper of weight g./m. coated on one side with a cellulose acetate film layer (approximately 50% by Weight of combined acetic acid) of a thickness of approximately 10 microns, which layer is aflixed to the paper by means of an adhesive and deacylated to a depth of-about 4 microns to an acetyl content calculated as combined acetic acid of on an average approximately 20% by weight (which corresponds to an average number of acyl groups per unit of glucose of the cellulose acetate of 0.7), is impregnated on the deacylated side of the cellulose acetate layer with the following solution:

4-benzoylamino 5-n-propoxy 2-N-ethoxycarbonyl N- methylanunobenzene diazonium chloride, zinc chlo- 15 Ethanol (96%) ml 250 Water m1 750 and dried.

The diazotype material thus obtained is very lightsensitive. A sheet of it is image-wise exposed and developed as described in Example III. The copy shows a violetblack image on a white background.

If in the above sensitizing liquid an equivalent quantity of 4-benzoylamino 2,5-dimethoxybenzene diazonium chloride, zinc chloride double salt, had been used, the lightsensitive material thus obtained would have been considerably less light-sensitive and would have had a lower developing speed.

The diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and converted with n-propyl bromide into 2-nitro 4-chloro l-propoxybenzene. The nitro group of this compound is reduced and the amino compound thus formed is benzoylated. The 5- chloro 4-nitro 2-propoxy N-benzoylaniline is brought into reaction with monomet'hylamine and then acylated with the ethyl ester of chloro-formic acid to form S-propoxy 4- benzoylamino Z-N-ethoxycarbonyl N-methylamino l-nitrobenzene, which compound melts at 124126 C. From this nitro compound the diazonium chloride, zinc chloride double salt, is obtained in the usual way.

Example XIV Sized natural tracing paper of weight 80 g./m. is sensitized with a liquid containing: 4-acetylamino 5-(4'-chloro)phenoxy Z-N-acetyl N- methylarninobenzene diazonium chloride, zinc chloride double salt g 63 Alum g 5 Rice Starch g 40 Gelatin g 2 Vinnapas H.60 ml 50 Water ml 950 and dried.

A sheet of the dry light-sensitive material is image-wise exposed and developed as described in Example VIII. The copy shows a brown image on a transparent background. The image has good absorption for UV. radiation, so that the copy is very suitable for use as an intermediate original.

The diazonium compound used in the example is prepared as follows: S-chloro 2(4-chloro)phenoxyaniline is acetylated and then nitrated. The 5(4-ch loro)phenoxy 4- acetylamino Z-chloro l-nitrobenzene thus formed is brought into reaction with monomethylarnine, after which the reaction product is acetylated. The melting point of the 5(4'-chloro)phenoxy 4 acetylamino 2-N-acetyl N-methy'lamine l-nitrobenzene thus prepared is 21 0212 C. This nitro compound is converted in the usual way into diazonium compound, which is obtained in the form of the zinc chloride double salt.

Example XV Sized natural tracing paper is pre-coated with an aqueous dispersion of colloidal silica, in which anionic dispersed polyvinyl acetate, such as Setamul N28 (from Synthese N.V., Katwijk aan Zee, Netherlands) is present as a binder, and dried. The paper thus pre-coated is sensitized with a liquid containing:

4-benzoylamino S-methoxy 2-N-acetyl N-methylaminobenzene diazonium chloride, zinc chloride tained is image-wise exposed under a transparent Indianink drawing until the diazonium compound under the image-free portions of the original has bleached out. The light-sensitive diazotype material is developed in ammonia vapour. The copy shows a red image on a clear background.

If in the above sensitizing liquid an equivalent quantity of 4-benzoylamine 2,5-dirnethoxybenzene diazonium chloride, zinc chloride double salt, had been used, the light-sensitive material thus obtained would have been considerably less light-sensitive and would have had a lower developing speed.

The diazonium compound used in the example is prepared as follows: S-chloro Z-methoxyaniline is successively benzoylated, nitrated, and brought into reaction with monomethylamine. The S-methoxy 4-benzoylamino Z-methylamino l-nitrobenzene thus obtained is acetylated. The nitro compound thus obtained melts at 206-208 C.

From this nitro compound the diazonium compound is prepared in the usual way, said compound being obtained in the form of the zinc chloride double salt.

Example XVI White paper coated with a so-called baryta layer is sensitized with a solution containing:

4 =benzoylarnino- 5 (4' chlorophenoxy) 2 N- acetyl N-methylaminobenzene diazonium chlo- A sheet of the diazotype paper thus obtained is imagewise exposed as described in Example XV and then developed with developer A.

The copy shows a violet-red image on a white background.

The diazonium compound used in the example is prepared as follows: S-chloro 2(4-chlorophenoxy)aniline is benzoylated and then nitrated. The 5-(4'-ch-loro)phenoxy 4-benzoylamino 2-chloro l-nitrobenzene is brought into reaction with monomethylamine, after which the reaction product is acetylated. The melting point of the 5-(4'-chloro)phenoxy 4-benzoylamino 2-N-acetyl N- methylamino l-nitirobenzene thus prepared is -182184 C. From [this nitro compound the diazonium compound is prepared in the usual way and obtained in the form of the zinc chloride double salt.

Example XVII White base paper of weight g./m. for the diazotype process is sensitized with a liquid containing:

4-benzoylamino S-cyclopentylo'xy Z-N-acetyl N- methyla-minobenzene diazonium chloride, zinc chloride double salt g 30 Citric acid g 5 Vinnapas H.60 ml 30 Water ml 970 and dried.

A sheet of the diazotype material thus obtained is image-wise exposed as described in Example II and then developed with developer A. The copy shows a darkbrown image on a foggy brown background.

Another sheet is also exposed as described in Example II and then developed with developer D. The copy shows a brown image on a foggy light-brown background.

The diazonium compound used in the example is prepared as follows: p-Chlorophenol is converted W t aid of cyclopenty} bromide into 4-chloro l cyclopentyh oxybenzene. This product is nitrated, the nitro group 18 subsequently reduced, and the amino group is benzoylated. The 2 -'beuzoy1amino 4-chlotro l-cyclopentyloxybem in which X is an anion; R is an alkyl, a cycloalkyl or an aralkyl radical; COR is an acyl group; R is an acylamino, an alkylsulphonamido, an aralkylsulphonamido, an arylsulphonamido or a 1,3,5 triazinyl group; and R is an alkyl, a cycloalkyl, an aralkyl or an aryl radical.

2. Diazotype material according to claim 1, wherein R is a nonbranched alkyl group having at most five C- atoms; R is an acylamino or 2. 1,3,5 triazinyl group; and R is an alkyl, an aralkyl or an aryl radical.

3. One-component diazotype material according to claim 1, wherein the diazonium compound is a compound of the general formula:

NgX

IIIH s in which R is a nonbranched alkyl group having at most five C-atoms; R is a hydrogen atom or an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group; R is an alkyl, alkyloxy, benzyl, benzyloxy, phenyl or phenoxy group; and R is an alkyl or a benzyl radical.

4. One-component diazotype material according [to claim 3, wherein R is an alkoxy, a benzyloxy or a phenoxy group.

18 5. A diazonium compound of the general formula:

(JO-R,

I Rs

in which X is an anion; R is an alkyl, a cycloalkyl or an aralkyl radical; COR is an acyl group; R is an acylamino, an alkylsulphonamido, an aralkylsulphonamido, an arylsulphonamid-o or a triazinyl group; and R is an alkyl, a cycloalkyl, an aralkyl or an aryl radical.

6. A diazonium compound according to claim 5 wherein R is a non branched alkyl group having at most five C-atoms; R is an acylamino or a triazinyl group; and R is an alkyl, aralkyl or aryl radical.

7. A diaoznium compound of the general formula:

NgX

in which R is a nonbranched alkyl group having at most five C-atoms; R is a hydrogen atom or an alkyl, an alkoxy, a benzyl, a benzyloxy, a phenyl or a phenoxy group; R is an alkyl, an alkyloxy, a benzyl, a benzyloxy, a phenyl or a phenoxy group; and R is an alkyl or a benzyl radical.

8. A diazonium compound according to claim 7 wherein R is an alkoxy, a benzyloxy' or a phenoxy group.

References Cited UNITED STATES PATENTS 2,198,827 4/1940 Leuch 96-9 1 2,326,782 8/1943 Jacobus et a1. 969l 2,529,029 11/1950 Lantz et a1. 96-9 1 2,665,985 1/ 1954 Sus 96-91 3,016,298 '1/1962J Sanders et a1. 96-91 OTHER REFERENCES Grant, Julius: Hackhs Chemical Dictionary, 3rd edition, McGraW-Hill, New York, 1944 (page 865 relied on).

NORMAN G. TORCHIN, Primary Examiner. C. L. BOWERS, Assistant Examiner. 

1. DIAZOTYPE MATERIAL WHICH COMPRISES A SUPPORT SHEET CARRYING A LAYER CONTAINING A DIAZONIUM COMPOUND OF THE GENERAL FORMULA: 